Since the existence of hierarchical pores can provide multiple advantages derived from each pore-size regime, hierarchical porous materials have been synthesized by many researchers. SBA-15 has obvious advantages such as good hydrothermal stability induced from thicker wall than that of MCM-41, and high surface area generated from mesoporous structures. Furthermore, when macropores are introduced in to the mesostructure of SBA-15, the material has additive advantages like ease access to active sites derived from macroporous structures. In this regard, meso/macroporous SBA-15 should be very attractive for their application in the area of adsorption, catalysis and separation. The meso/macroporous SBA-15 were prepared by a new and simple dual-templating method, which is the combination of replicating the closed packed array of colloidal crystal and liquid crystal mesophase of surfactant. The meso/macroporous silicate can be successfully synthesized without losing unique properties of each pore size regime. With the PS:Si ratio, not only was the volume of macroporous space increasing, but also the macrostructures was better ordered. The adsorption dynamics were also improved with the increase in the volume of macroporous space. This result seems to confirm that the macropores in mesoporous silicates really provide an easy access to active sites.